Hydroaromatic sulfonates and their preparation



Patented Dec. 7, 1948 1 PATENT" OFFICE nrncoesomrlc sUtFoNArEs Amman;

rngrARA'rIoN HansrSohindier, Evanstom lllaassig npn to The Rain 7 0.15.

I; Qqmnann asa; 111,, a? cm pcr ticn No*Drawing-. -Application"ctobcr23,1944,

Serial No. 56,0;0145" 9 Claims. (01. ma ts),

The object of this'inventi'on is to provide noveli-indanylphenyI-a-decalin Dicyclchexyltetralin ice an:ammat c:hydreca borwith the y c. e-'- finlunsa ura s. nthem; hyd oca bon n the presence ofcold sulfuric acidor aluminum chloide Aswanample, n} the prep ration f Iindanylcralchexr en -cycloh xy b z an be condensed with indene n thepresence-of aluminum chloride, Asanpther example, in the preparation of4-indanylphenyl-a-decalin, alphaphenr ideca in s prepa ed by first' ns ne zen with; q taht' r naph h n and t e ondens ng the:a phaapheny decalmwith dene usin aluminslm hl r deas condensat o a alysfi' I I In thepreparation of dlcyclohexyltetralin, cyclohexyltetralin is firstprepared-- bycondensation of a molecular excess oftetralin with cyclohex-Lane: in. the presence of cold; sulfuric acid" followed by;condensation of: the cyelohexyltetralin with cyclohexanein the presenceof aluminum chloride, reaction being carried out in a solutionof-pyclohexane at a temperature of approximately: 65,;- F.

"In order -to illustrate the invention sulfonated cyclohexylt'etralinwas: prepared by adding 82 grams of cyclohexenet'oa mixture of396.2'grams of tetralin and 92 grams of concentrated sulfuric acidmaintained in a coolingbath at a temperature of 41-50" F". The mixturewas constantly stirred while: the cyclohexane was added over a period"of 1%. hours. Stirring was continued after the addition of all thecyclohexene for one hour without cooling, and the temperature reached.86 1. The hydrocarbon layerwas then separated from-the acid andwashedtwice with cold concentrated sulfuric acid; and then washed with Water,followed by dilute causitc soda solution and again washed with Water.The resulting hydrocarbon was distilled to remove unreacted tetralin.134 grams of material boiling above 446 F. was obtained representing ayield of 62.6% of theoretical yield. The reaction product was determinedto have the following characteristics The molecular weight ofcyclohexyltetralin is 214,

thus indicating that the hydrocarbon product is not purecyclohexyltetralin.

The product was then sulfonated with concentrated sulfuric acid in theproportion of grams of hydrocarbon to 138 grams cc.) of concentratedsulfuric acid. The mixture was stirred for one hour without any attemptto control the temperature and the temperature rose to F.

The sulfonated mixture was then mixed with 500" cc. of water, andsulfonic acid separated as an upper layer with a strong bluefluorescense. f The sulionic acid was separated from themixture,

chloride as the condensation catalyst and sulmixed with cc. of Water andmade alkaline with sodium hydroxide. The alkaline solution was thenfiltered and evaporated to dryness. The residue was taken up in ether inorder to dissolve the sodium sulfonates and the insoluble sodium sulfatewas filtered oil. The sodium sulfonates were recovered from the ethersolution by evaporating the ether. 55 grams of purified sodium sulfonatewas thus obtained corresponding to 80.5% of theoretical yield based onthe hydrocarbon subjected to sulfonation. The free su1-' fonic acid wasprepared from the sodium sulfonate by acidification with anhydrous HCl.This material was determined to have a molecular weight of 290 asagainst a calculated molecular weight of 294.

An emulsifiable oil was prepared by mixingtogether 74.7% by weight ofmineral oil, 13.7% by weight of sodium sulfonate prepared as justdescribed, 2.2% by weight of diethylene glycol, 5.5% by weight of oleicacid and 2.7% by weight of 20% caustic soda solution. The compositiongave a stable emulsion and was satisfactory for use as a soluble cuttingoil.

The mineral oil used in the above-described composition was a Westernneutral having a viscosity of 100 seconds Saybolt at 100 F.

Sulfonic acids, or sulfonates'prepared in accordance with my inventionare useful, in general, as emulsifying agents and detergents andwherever a surface active materialis useful, but are specially useful inthe preparationof soluble oils for cutting and similar purposes.

It is claimed:

1. The method of preparing a surface active compound comprisingcondensing .indene with benzene in which one hydrogen is substitutedwith a hydroaromatic radical and sulfonating the resulting product.

2. Method in accordance with claim 1 in which the condensation iscarried out in the presence of aluminum chloride as the catalyst.

3. Method in accordance with claim 1 in which fonating the resultingcondensation product. 6. The method of preparing a surface activecomposition comprising condensing alphaphenyl-decalin with indene in thepresence of aluminum chloride as catalyst and sulfonating the resultingcondensation product.

7. The sulfonated compound in which R is a hydroaromatic group.

8. Compound in accordance with claim which R is the cyclohexyl radical.9. Compound in. accordance with claim 7 in which R is theoctahydronaphthyl radical. I 1 HANS SCHINDLER.

REFERENCES CITED The following references'are of record in'the file ofthis patent: i

UNITED STATES PATENTS Number Name 1, Date 1,750,198 Schrauth Mar. 11,1930 1,758,277 Daimler May 13,1930 1,787,408 Pospiech Dec.. 30, 19301,988,832. De Groote -Jan;.22, 1935 2,028,271 Brodersen Jan. 21, 19362,054,140 Segessemann Sept. 15, 1936 2,076,166 Segessemann Apr. 6, 19372,199,776 Becherer May 7, 1940 2,202,686 Borglin May 28, 1940 FOREIGNPATENTS Number Country Date 263,873 Great Britain May 31, 1928 438,466Germany May 8, 1930 364,537 Great Britain Dec. 22, 1931 416,379 GreatBritain a. Sept. 6, 1934 OTHER REFERENCES Beilstein, Handbuch der. Org.Chem.," 4th Ed., vol. XI, pp. 154,

Beilstein, Handbuch der. Org. Chem," 4th Ed., Suppl. vol. XI/XII, p. 43.

Certificate of Correction I Patent No. 2,455,811. December 7, 1948.

HANS SOHINDLER It is hereby certified that errors appear in the printedspecification of the above numbered patent requiring correction asfollows:

Column 2, lines 16 and 17, 19, 29, for cyelohexane read cyclohezene;

and that the said Letters Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Office.

Signed and sealed this 22nd day of March, A. D. 1949.

THOMAS F. MURPHY,

